Towards an understanding of thermally activated self-healing of an ionomer system during ballistic penetration

The self-healing phenomenon exhibited by the ionomer known as Surlyn 8940 (DuPont), a partially neutralized poly(ethylene-co-methacrylic acid) random co-polymer, during high-energy impact has been investigated here according to three separate strategies. The first consisted of a post-mortem scanning electron microscopy examination of impact surfaces of actual ballistic impacts for a range of bullets with different shapes, sizes and velocities. A complex range of competing and/or complementary processes based upon elastic and viscous responses was observed. The elastic response to impact provides for a polymer rebound or shape memory effect, while the viscous response provides for the final sealing of the cavity and is dependent upon the level of thermal frictional forces transferred during impact. The balance of these influences determines healing, and is shown to be altered by the size and shape of the bullet or indeed by the polymer morphology itself. The second strategy investigated the healing mechanism using a method that mimics the elastic response to impact in a controlled environment. This work highlighted the importance of the ionic clusters present in the ionomer and the gradient of viscoelastic properties formed at varying distances from the impact zone particularly when compared to non-ionic polymers. The repeatability of elastic healing was demonstrated, and reinforced the notion that healing arose from the inherent polymer structure of the ionomer. The third strategy investigated the role of the viscous response during impact and found that increased molecular mobility in the melt was critical to achieving optimal healing, although again the ionic clusters were found to be critical to maintaining sufficient structural integrity and preventing excess viscous flow.

[1]  H. Tachino,et al.  Dynamic mechanical relaxations of ethylene ionomers , 1993 .

[2]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.

[3]  E. W. Meijer,et al.  Supramolecular polymers at work , 2004 .

[4]  Simon A. Hayes,et al.  A self-healing thermosetting composite material , 2007 .

[5]  Robert B. Moore,et al.  A new multiplet-cluster model for the morphology of random ionomers , 1990 .

[6]  S. V. D. Zwaag Self healing materials : an alternative approach to 20 centuries of materials science , 2007 .

[7]  A. Eisenberg Clustering of Ions in Organic Polymers. A Theoretical Approach , 1970 .

[8]  R. Register,et al.  Low-shear melt rheology of partially-neutralized ethylene-methacrylic acid ionomers , 1996 .

[9]  Thomas C. Ward,et al.  Self-Healing of Poly(Ethylene-co-Methacrylic Acid) Copolymers Following Projectile Puncture , 2007 .

[10]  N. Sottos,et al.  Microcapsule induced toughening in a self-healing polymer composite , 2004 .

[11]  Thomas C Ward,et al.  Thermal characteristics of the self-healing response in poly(ethylene-co-methacrylic acid) copolymers , 2007, Journal of The Royal Society Interface.

[12]  D. Wu,et al.  Self-healing polymeric materials: A review of recent developments , 2008 .

[13]  S. Zwaag,et al.  Development of a quasi-static test method to investigate the origin of self-healing in ionomers under ballistic conditions , 2008 .

[14]  N. Sottos,et al.  Fracture testing of a self-healing polymer composite , 2002 .

[15]  A. Eisenberg,et al.  Sizes and stabilities of multiplets and clusters in carboxylated and sulfonated styrene ionomers , 1992 .

[16]  H. Makowski,et al.  Viscoelastic Behavior of Sulfonated Polymers: Sulfonated Ethylene-Propylene Terpolymer , 1980 .

[17]  S. White,et al.  Self-activated healing of delamination damage in woven composites , 2001 .

[18]  Hitoshi Yamamoto,et al.  Order-disorder transition of ionic clusters in ionomers , 1989 .

[19]  Robert B. Moore,et al.  Small-angle X-ray scattering investigations of ionomers with variable-length side chains , 1991 .

[20]  Jr. Stephen James Kalista Self-Healing of Thermoplastic Poly(Ethylene-co-Methacrylic Acid) Copolymers Following Projectile Puncture , 2004 .

[21]  L. Alexander,et al.  X-ray diffraction methods in polymer science , 1969 .

[22]  S. Varghese,et al.  Metal-ion-mediated healing of gels , 2006 .

[23]  R. Jerome,et al.  Direct NMR evidence for a local restriction in the segmental chain mobility of a model ionomer , 1994 .

[24]  C. Bowman,et al.  Photoinduced Plasticity in Cross-Linked Polymers , 2005, Science.

[25]  R. J. Jackman,et al.  Filler and Percolation Behavior of Ionic Aggregates in Styrene-Sodium Methacrylate Ionomers , 1994 .

[26]  S. Hayes,et al.  Self-healing of damage in fibre-reinforced polymer-matrix composites , 2007, Journal of The Royal Society Interface.

[27]  R. Fall Puncture Reversal of Polyethylene Ionomers - Mechanistic Studies , 2001 .

[28]  A. Eisenberg,et al.  Ion Clustering and Viscoelastic Relaxation in Styrene-Based Ionomers. II. Effect of Ion Concentration , 1973 .